Alkynoxy acids



United Stag a n O ALKYNOXY ACIDS Henry Brown, Huntington Woods, Donald .H. Becking, Detroit, and Thaddeus W. Tomaszewski, Dearborn, Mich., assignors to The Udylite Research Corporation, Detroit, Mich., a corporation of. Michigan No Drawing. Application October 4, 1955 Serial N0. 538,529

7 Claims. (Cl.260431) 2,841,602 Patented July 1, 1958 ion was replaced by nickel ion with one pass throughthe cationic exchange bed (a polystyrene nuclear sulionic resin bed). i

Analysis.Calculated for- C H SO Na: C, 32.25; H,

5 3.76; s, 17.20. ound; c, 52.4;11, 3.5; s, 17.0.

fonic acids of 3 to 14 carbon atoms inclusive and alkynoxy carboxylic acids of 5 to 15 carbon'atoms, andtheir salts, which have technological value, for example, in plastics as monomers, in the formation of water-soluble high molecular weight resins, as acid pickling inhibitors, as dying assistants, as scavengers for hydrogen chloride and hydrogen bromide, in chlorinated or brominated solvents. A more particularobject is to provide a new class ofanionic addition agents (especially the alkynoxy sulfonic acids and their salts) that are useful in electroplating, especially in bright nickel plating. H 7

.The aboveobjects are accompl' h d according to the present invention by providing a new class of unsaturated acids and their salts, consisting of alkynoxy alkane-, sul-- the salts thereof, all of which are exemplified in Table I.

The alkane group in these acids contains from 1 to 4 carbon atoms.

The starting materials for the preparation ofthealkynoxy acids (and their salts) of this invention are, for:

METHOD '1 An alkyne alcohol or glycol, a. halo-alkane sulfonic acid or carboxylic acid (or sodium or potassium salt) in which the alkane group is not greater than butane, and

sodium, potassium, or lithium hydroxide inwater so'lution. These materials are refluxed for about 2 to 20' hours (preferably 3 to 10 hours and the solution treated with activated carbon and filtered. If the dried salt is desired, the solution is acidified and evaporated to dryness and extracted with alcohol and the alcohol is then evapcrated The white ly tan 'salt of the alkyn v I V oxy acid is then obtained. v v 1.

Example 1 of Method The preparation of 2-propynoxy 1-ethane sulfonic acid' (Na salt) i. e. HCEC-CH OC H SO Na.

Propargyl alcohol (1 mole),"sodiurn. 2-bromoethane sulfonate BrC H SO Na (1 mole), sodium hydroxide (1 mole) in water to make about a 20% solution, were refluxed for 6 hours. The solution wasthen treated with activated carbon and filtered. to give a pale brown solution containing the 2-propynoxy-1-ethane sodium sulfonate. When this solution was filtered through a cationic exchange resin previously. treated with a soluble "nickel 7 salt such as nickel chloride, most (75%) of the sodium' ionic acids of 3 to 14 carbon atoms .inclusive, and a1kyn-14 oxy alkane carboxylic acids of 5 to 15 carbon-atoms and about 8 hours.

, ,.su1fonate.

Example 2 of Method 1 The preparation of 2-propynQXy-1-acetic acid (Na salt), HCEC-CH OCH COONa.

Propargyl alcohol (1 mole), mono-chloroacetic acid (1 mole), and sodium hydroxide to give a 10 to 20% aqueous caustic solution, is refluxed for -about 3 hours. The solution is filtered with activated carbon and contains 2-propynoxy-1-acetic acid (Na salt) dissolved there- Example 3 of Method 1 The preparation of 2-butynoxy-1,4-diacetic acid (Na salt), Na0OCCH OCH -C- =C-CH OCH COONa.

Z-butyne 1,4 diol (1 mole), monochloroacetic acid (2 moles), sodium hydroxide (2 moles) dissolved in water'to give a 10 to 20% caustic solution are refluxed for about 3 hours. The solution is treated with activated carbon and filtered giving an aqueous solution of Z-butyn- "oxy-l,4-diacetic acid (Na salt).

1 2 METHOD 2 An admixture is made of an alkyne halide, a hydroxy alkane sulfonic acid (Na or K salt) in which the alkane group isnot greater than butane, and sodium, lithium or potassium hydroxide in water solution. These materials are refluxed for about 2 to 20 hours (preferably 3 to 10 hours) and then the solution is treated with activated carbon and filtered to give a water solution of the alkynoxy alkane sodium sulfouate.

7 Example 1 of Method 2 The preparation of 2-propynoxy-1-ethane sulfonic acid (Na salt). Isethionic acid (Na salt) HOC H SO Na :(1 mole), propargyl bromide (1 mole), andl mole sodium hydroxide in about 20% strength are refluxed for V V V Thesolution is treated.with activated carbon and filtered to give a water solution of Z-pr'opy'noxyd-ethane sulfonicacid (Na salt). a

Example 20 Method a The preparation of 2-bi1tynsx -1,4-ai-eth 1i sulfonic acid (Na salt), v V v r v NaO SC- H OCH C= C-QH OC H SO Na Isethionic acid (Na salt) 2 moles), 1,4-dichloro but'yne- 2 (1 mole and 1 mole of sodium hydroxide in about a 20% water solution are refluxed for about 8 hours. 'The solution is treated with activated carbon and filtered to give a water solution of 2-butynoxy-1,4di ethane sodium METHOD I An alkyne'alcohol'or glycolra di-halo alkane inwhich the alkane group is not greater than butane, and sodium, potassium or lithium hydroxide in water solution are re- .fluxed. for about 3 to 20 hours, sodium sulfite is then added, and the solution refluxed for an additional 4 to 20 hours. The solution is then treated with activated carbon and hydrogen peroxide (to oxidize, any excess of sodium sulfite). The solution is then Qfiltered to give a pale brown solution which contains the alkynoxy alkane sodium" sulfonate. The dried white sodium salt can be obtained as outlined in Method 1.

Example 0].Method 3 1 The preparation of l-methyl, l -ethyl-Z-piopynoxy-lethane sulfonic acid (Na .salt). Methyl pentynol' (1 mole), ethylene dibromide (1 mole), sodium hydroxide (1 mole) in 20% aqueous solution were refluxed for 4 hours, then 1 mole of sodium sulfite was added and the solution refluxed for an additional 6 hours. The solution was then treated with activated carbon and hydrogen peroxide (or sodium peroxide) to oxidize any excess of sulfite remaining. The solution was then filtered to give a pale brown solution containing l-methyl, 1-ethyl-2-propynoxy-l-ethane sulfonic acid (Na salt),

An alkyne alcohol or glycol, a di-halo alkane in which the alkane group is not greater than butane, and sodium, potassium or lithium hydroxide solution are refluxed for about 3 to 8 hours, and the insoluble oil separated off. The oil is then refluxed with concentrated sodium sulfite solution for about 4 to 20 hours. This gives, after treatment with activated carbon and hydrogen peroxide, a pale yellow or pale brown solution containing the alkynoxy alkane sodium sulfonate.

Example 1 of Method 4 The preparation of 2-butynoxy-l,4-diethane sulfonic acid (Na salt). Butyne-1,4-diol (1 mole), ethylene dibromide (2 moles) and sodium hydroxide (1 mole) in about 20% solution are refluxed for about 6 hours and the solution cooled and the heavy oily brown liquid which separates to the bottom is drawn E. The yield is about 60% on the first run, but with re-use of the water solution for the second batch the yield is increased to about 80%. The oily liquid is then reacted with 1.75 moles of sodium sulfite in a saturated water solution, by refluxing for about 4 to 6 hours, and the solution is then treated with activated carbon and hydrogen peroxide and filtered to give a pale yellow solution of the 2-butynoxy1,4, diethane sodium sulfonate with allyl sulfonic acid and o-benzoyl sulfimide and benzene sulfonic acid. For example:

(approximately 10 to 100 amps/sq. ft).

The higher the solution agitation density that can be used.

The butynoxy ethane sulfonic acids (or their nickel or sodium salts, etc.) are also good additives for obtaining bright ductile nickel plate when used in place of the propynoxy ethane sulfonic acids in the above formulation.

The amine salts of the alkynoxy acetic acids such as propynoxy acetic acid and butynoxy acetic acids used in a concentration of about 1 to 2 grams/liter are good scavengers for hydrogen chloride and good stabilizers for trichloroethylene. V

The alkynoxy sulfonic acids and carboxylic acids are of value as acid pickling inhibitors when used in a concentration of about 1 to 3 grams/liter.

What is claimed is:

1. An unsaturated aliphatic acid selected from the group consisting of alknoxy sulfonic acids having 3 to 14 carbon atoms inclusive, alknoxy carboxylic acids having 5 to 15 carbon atoms and the sodium, potassium,

the higher the current nickel, cobalt, iron, magnesium, ammonium, mercury I TABLE L-ALKYNOXY SULFONIO AND ALKYNOXY OARBOXYLIC COMPOUNDS 8. HCEC-(XCHzh-OCHLS 01H 8. HO-CHz-CEO-CHzO Cal-14S 0 9. HO-OHn--CEOOH2OOH2COOH OHaCOOH HO-OHn-CEG-OHzO- H-COOH HCEU-CKOHa) (CzHs) OC:H4SOzH HCEC-OHzOCHzCOOH HOzS-CzILOOHa-CEO-CHzOCaILS OaH HOOO-OHz-OCHg- EO-CHgOOHzCOOH HO-OH:OECCH1OOCOOH (Na K Ni 00 Fe Mg N'Pn, H amine 'salt 0. (Na, K, Ni, Co, Fe, Mg, NH Hg, amine salts etc. (Na, K, Ni, 00, Fe, Mg, NHi, Hg, amine salts 0.) (Na, K, Ni, 00, Fe, Mg, N114, Hg, amine salts etc.) (Na K, Ni, 00, Fe, N Hg, amine salts etc.) (Na, K, Ni, 00, Fe, Mg, NHi, Hg, amine salts etc. (Na, K, Ni, Co, Fe,'Mg, NH4, Hg, amine salts etc.

(Na, K, Ni, 00, Fe, Mg, htlHi, Hg, amine salts e 0. (Na, K, Ni, 00, Fe, Mg, NH Hg, amine salts 0. (Na, K, Ni, 00, Fe, Mg, NH) Hg, amine salts etc.

(Na, K, Ni, 00, Fe, Mg, lgflt, Hg, amine salts e 0.

(Na, K, Ni, 00, Fe, Mg, 12TH) Hg, amine salts e e.

The sodium, potassium or lithium salts or the nickel salts of the propynoxy ethane sulfonic acids are very good additives for obtaining bright ductile plate from acidic and amine salts thereof, said acids containing an alkane group having from 1-4 carbon atoms.

2. An unsaturated aliphatic acid selected from the nickel baths of the Watts type when used in conjunction class consisting of alkynoxy alkane sulfonic acids having 6 3 to 14 carbon atoms inclusive, alkynoxy alkane carthe sodium, potassium, nickel, cobalt, iron, magnesium, boxylic acids and their salts having 5 to 15 carbon atoms ammonium, mercury and amine salts thereof. and the sodium, potassium, nickel, cobalt, iron, magne- 6. Z-propynoxy-l-acetic acid sium, ammonium, mercury and amine salts thereof, the alkane group of said acids containing 1 to 4 carbon 5 (HCTC QHZOCHZCOQH) t the sodium, potassium, nickel, cobalt, iron, magnesium,

ammonium, mercury and amine salts thereof.

7. 2-butynoxy-1,4-di-acetic acid 3. 2-propynoxy-1-ethane sulfonic acid (HCEC-CH OC H SO H) the sodium, potassium, nickel, cobalt, iron, magnesium, 10

ammonium, mercury and amine salts there f, the sodium, potassium, nickel, cobalt, iron, magnesium,

4. 1,l-dimethyl-Z-propynoxy-l-ethane s lf i id ammonium, mercury and amine salts thereof.

(HCEO C(CH3)-=OC2H4SO8H) References Cited in the file of this patent the sodium, potassium, nickel, cobalt, iron, magnesium, 15 UNITED STATES PATENTS ammonium, mercury and amine salts thereof.

2,170,380 Holsten Aug. 22, 1939 5. 2-butynoxy 1,4d1 ethane sulfomc acid 2,352,461 walker June 27, 1944 

1. AN UNSATURATED ALIPHATIC ACID SELECTED FROM THE GROUP CONSISTING OF ALKNOXY SULFONIC ACIDS HAVING 3 TO 14 CARBON ATOMS INCLUSIVE, ALKNOXY CARBOXYLIC ACIDS HAVING 5 TO 15 CARBON ATOMS AND THE SODIUM, POTASSIUM, NICKEL, COBALT, IRON, MAGNESIUM, AMMONIUM, MERCURY AND AMINE SALTS THEREOF, SAID ACIDS CONTAINING AN ALKANE GROUP HAVING FROM 1-4 CARBON ATOMS. 